JPH01294521A - Production of aqueous colloid dispersion of rare earth element compound and product - Google Patents
Production of aqueous colloid dispersion of rare earth element compound and productInfo
- Publication number
- JPH01294521A JPH01294521A JP63228911A JP22891188A JPH01294521A JP H01294521 A JPH01294521 A JP H01294521A JP 63228911 A JP63228911 A JP 63228911A JP 22891188 A JP22891188 A JP 22891188A JP H01294521 A JPH01294521 A JP H01294521A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- earth element
- colloidal dispersion
- oxide
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 49
- 239000000084 colloidal system Substances 0.000 title claims description 14
- 150000001875 compounds Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000006185 dispersion Substances 0.000 title claims description 4
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000001246 colloidal dispersion Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- -1 rare-earth compound Chemical class 0.000 claims abstract description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 9
- 239000012736 aqueous medium Substances 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 8
- 239000012429 reaction media Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical group O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000010908 decantation Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 3
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 150000002412 holmium compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000010414 supernatant solution Substances 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0008—Sols of inorganic materials in water
- B01J13/0013—Sols of inorganic materials in water from a precipitate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Colloid Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、希土類元素化合物を水性媒質中に分散させて
なるコロイド分散体の製造方法に関する。さらに詳しく
は、本発明は、イツトリウム族希土類元素化合物のコロ
イド分散体の製造方法に関する。また、本発明は新規工
業製品としての、前記方法で得られる生成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a colloidal dispersion in which a rare earth element compound is dispersed in an aqueous medium. More specifically, the present invention relates to a method for producing a colloidal dispersion of a yttrium group rare earth element compound. The invention also relates to the products obtained by the method as new industrial products.
なお、本発明を説明するにあたって、「イツトリウム族
希土類元素」とは、希土類元素のうちのより重い元素、
即ち原子番号に従って、サマリウムから始ってルテチウ
ムで終る希土類元素、そしてイツトリウムを含めたもの
をいう。In explaining the present invention, "yztrium group rare earth elements" refer to heavier elements of rare earth elements,
That is, according to their atomic numbers, rare earth elements start with samarium, end with lutetium, and include yttrium.
［従来の技術及びその問題点］
米国特許第３，０２４．１９９号によれば、（ａ）１価
希土類元素塩の水溶液をアンモニアと接触させて対応す
る水和した希土類元素酸化物を沈殿させ、
（ｂ）アンモニウム塩の大部分をアンモニアによって除
去し、その際にｐＨを９．５〜１０．５に維持するよう
にし、
（ｃ）水和した希土類元素酸化物を分離し、次いでこれ
を６０〜１００℃の温度範囲で加熱することによって解
凝させる
ことからなる方法によって水和した希土類元素酸化物の
水性ゾルを製造する方法が提案されている。[Prior Art and Problems Therewith] According to U.S. Pat. No. 3,024.199, (a) an aqueous solution of a monovalent rare earth element salt is contacted with ammonia to precipitate the corresponding hydrated rare earth element oxide; (b) removing most of the ammonium salts with ammonia, maintaining the pH between 9.5 and 10.5; (c) separating the hydrated rare earth oxides, which are then A process has been proposed for producing an aqueous sol of hydrated rare earth element oxides by a process consisting of peptization by heating in the temperature range from 60 to 100<0>C.
この方法で得られた水和希土類元素のゾルは、希土類元
素酸化物として表わして１０〜５０重量％の濃度を示し
、その粒子のサイズは５〜２００ｍμであってその長さ
／直径の比は約ｌ：１〜５・１であり、７．０〜８．３
のｐＨを有し、安定化用の１価陰イオンを含有する。そ
して、希土類元素酸化物／安定化用１価陰イオンのモル
比は６．６：１〜１６５：１である。The hydrated rare earth element sol obtained by this method has a concentration of 10 to 50% by weight expressed as rare earth element oxide, the particle size is 5 to 200 mμ, and the length/diameter ratio is Approximately l: 1-5.1, 7.0-8.3
It has a pH of , and contains stabilizing monovalent anions. The molar ratio of rare earth element oxide/stabilizing monovalent anion is 6.6:1 to 165:1.
したがって、このゾルは真の希土類元素水酸化物の式に
近似した式を有する水和した希土類元素酸化物のゾルで
ある。Therefore, this sol is a hydrated rare earth oxide sol with a formula approximating that of a true rare earth hydroxide.
［発明が解決しようとする課題］
このように、多くの工程を有し、そして多量のアンモニ
アを使用して新たに製造されかつ取扱いが困難な水和し
た希土類元素酸化物に頼る従来技術の方法に対して、本
発明は、希土類元素化合物を水性媒質中に分散させてな
るコロイド分散体（以下ではこれを「ゾル」と称する）
の非常に簡単な製造方法を提案することである。[Problems to be Solved by the Invention] As described above, the prior art method involves many steps, uses a large amount of ammonia, is newly manufactured, and relies on a hydrated rare earth element oxide that is difficult to handle. In contrast, the present invention provides a colloidal dispersion (hereinafter referred to as a "sol") formed by dispersing a rare earth element compound in an aqueous medium.
The purpose is to propose a very simple manufacturing method.
［課題を解決するための手段］
本発明の製造方法は、希土類元素酸化物を２．５〜５．
０の間のｐＫａを有する水溶性の１価の酸の所定量と反
応させ、次いで得られた反応媒質を加熱することからな
ることを特徴とする。[Means for Solving the Problems] The production method of the present invention provides a rare earth element oxide with a concentration of 2.5 to 5.
It is characterized in that it consists in reacting with a predetermined amount of a water-soluble monovalent acid having a pKa between 0 and then heating the reaction medium obtained.
本発明の方法によれば、後述するような特性を持つゾル
を直接得ることができる。According to the method of the present invention, a sol having the characteristics described below can be directly obtained.
しかして、本発明の方法に係るのは、一般にミニ酸化物
形である希土類元素酸化物である。Thus, the method of the invention concerns rare earth oxides, which are generally in mini-oxide form.
好ましくは、イツトリウム族希土類元素の酸化物、さら
に好ましくは酸化イツトリウムＹ２０．及び酸化ホルミ
ウム）Ｉｏｔａｓが使用される。Preferably, an oxide of a rare earth element of the yttrium group, more preferably yttrium oxide Y20. and holmium oxide) Iotas are used.
使用する酸化物は好ましくは９９％以上の高純度である
ことが望ましく、特に９９．９９％の純度を有する酸化
物が使用される。The oxide used preferably has a high purity of 99% or more, and in particular, an oxide having a purity of 99.99% is used.
希土類元素酸化物は微細粉末状であって、その粒子のサ
イズは数ミクロンであり、またその平均直径は多くの場
合１〜５μｍの間にある。ここで、平均直径とは、粒子
の５０重量％がこの平均直径よりも大きいか又は小さい
直径を有するような直径として定義される。Rare earth element oxides are in the form of fine powders, the particle size of which is several microns, and the average diameter of which is often between 1 and 5 μm. Here, the average diameter is defined as the diameter such that 50% by weight of the particles have a diameter that is greater or less than this average diameter.
本発明の方法の好ましい別法は、８５０℃〜１０５０℃
の間、好ましくは約９５０℃の温度に焼成した希土類元
素酸化物を使用することからなる。A preferred alternative to the method of the invention is 850°C to 1050°C.
using a rare earth element oxide calcined to a temperature of preferably about 950°C.
この焼成時間は、好ましくは２〜４時間である。This firing time is preferably 2 to 4 hours.
酸に関しては、その選択はそれが水溶性であり、１価で
ありかつ２．５〜５．０の間のｐＫａを示さねばならな
いことによって決められる。As for the acid, its selection is dictated by it having to be water-soluble, monovalent and exhibit a pKa between 2.5 and 5.0.
本発明の方法の実施にあたっては酢酸が全く好ましい。Acetic acid is highly preferred in carrying out the process of the invention.
また、不純物を含まない酸が使用される。酸の初期濃度
は重要ではなく、例えばＩＮに希釈されたもの又は１７
Ｎまでの濃縮されたものを使用することができる。一般
に、酸の溶液の濃度は１〜４Ｎの間で選ばれる。なぜな
らば、酸溶液は、希土類元素酸化物の分散媒をなし、し
たがって良好な攪拌条件下で浸蝕を行うのに十分に大き
い液相を構成すべきであるからである。Also, an acid free of impurities is used. The initial concentration of the acid is not critical, e.g. diluted in IN or 17
Enriched up to N can be used. Generally, the concentration of the acid solution is chosen between 1 and 4N. This is because the acid solution acts as a dispersion medium for the rare earth oxides and therefore should constitute a liquid phase large enough to carry out the erosion under good stirring conditions.
酸の使用量は本発明の方法の重要な要素である。この使
用量は化学型論的な量と比べて不足しているべきである
。このことは、使用する酸と金属陽イオンとして表わし
た希土類元素酸化物とのモル比が２．５〜１であること
を意味する。The amount of acid used is an important factor in the process of the invention. This amount used should be insufficient compared to the chemotypic amount. This means that the molar ratio of the acid used to the rare earth oxide expressed as metal cation is between 2.5 and 1.
その下方限界は良好な反応率及び良好な反応速度という
経済的な要求を考慮して決められる。The lower limit is determined by taking into account the economic requirements of good reaction rate and good reaction rate.
好ましくは、上記のモル比は１．１〜２．２、さらに好
ましくは１．２〜１．８の間で選定される。Preferably, the above molar ratio is selected between 1.1 and 2.2, more preferably between 1.2 and 1.8.
本発明の一実施態様によれば、前記した濃度に相当する
ように濃度を調節した酸の溶液に希土類元素酸化物が添
加される。According to one embodiment of the present invention, the rare earth element oxide is added to a solution of acid whose concentration is adjusted to correspond to the concentrations mentioned above.
他の実施態様によれば、希土類元素酸化物は水に懸濁さ
れ、次いで適切な量の酸が添加される。According to another embodiment, the rare earth oxide is suspended in water and then a suitable amount of acid is added.
この操作は二つの場合とも攪拌下に周囲温度（多くの場
合１５℃〜２５℃の間である）で行われる。This operation is carried out in both cases under stirring and at ambient temperature (often between 15°C and 25°C).
本発明の方法の第二工程は、反応混合物を５０℃から反
応媒質の還流温度までの間の温度で熱処理に付すことか
らなる。好ましくは、熱処理は７０℃〜１００℃で行わ
れる。The second step of the process of the invention consists in subjecting the reaction mixture to a heat treatment at a temperature between 50° C. and the reflux temperature of the reaction medium. Preferably, the heat treatment is carried out at 70°C to 100°C.
熱処理時間は非常に変動し得るものであって、温度が高
いほど短い。The heat treatment time can be highly variable, being shorter at higher temperatures.
反応温度になったならば、この温度は１〜４時間、好ま
しくは３〜４時間維持される。Once the reaction temperature is reached, this temperature is maintained for 1 to 4 hours, preferably 3 to 4 hours.
しかして、希土類元素化合物のゾルの生成が認められる
が、希土類元素酸化物を７０℃よりも低い温度で処理し
たときには反応しなかった希土類元素酸化物から実質上
酸る残渣が存在し得ることが認められる。Although the formation of a sol of the rare earth element compound is observed, when the rare earth element oxide is treated at a temperature lower than 70°C, there may be a substantial acidic residue from the unreacted rare earth element oxide. Is recognized.
本発明の好ましい別法は、この残渣を液−液分離技術、
即ち濾過、デカンテーション又は遠心分離によって分離
することからなる。A preferred alternative method of the invention is to process this residue using liquid-liquid separation techniques.
ie separation by filtration, decantation or centrifugation.
この分離は好ましくは遠心分離によって行われ、そして
希土類元素化合物を水性媒質中に分散させてなるコロイ
ド分散体が回収される。This separation is preferably carried out by centrifugation and a colloidal dispersion of the rare earth compound dispersed in an aqueous medium is recovered.
本発明に従えば、希土類元素化合物は水に分散されたコ
ロイド分散体の形で存在する。このことは、希土類元素
化合物がコロイド寸法の粒子を有するがしかしこれがイ
オン形の希土類元素の存在を排除するものではないこと
を表わしている。According to the invention, the rare earth element compound is present in the form of a colloidal dispersion dispersed in water. This indicates that the rare earth compound has particles of colloidal size, but this does not exclude the presence of the rare earth element in ionic form.
コロイド形の希土類元素の割合は好ましくは８５〜１０
０％である。The proportion of rare earth elements in colloidal form is preferably 85-10
It is 0%.
この分散体は、希土類元素酸化物として表わして１モル
／βにもなり得る希土類元素化合物濃度を示すことがで
きる。This dispersion can exhibit concentrations of rare earth compounds, expressed as rare earth oxides, which can be as high as 1 mol/β.
そのｐＨは中性附近にあり、より詳しくいえば６．０〜
７．５の間にある。Its pH is around neutral, more specifically 6.0~
It is between 7.5 and 7.5.
コロイドの化学組成は、分散体の遠心分離後に得られる
残留物について、ＥＤＴＡによる錯滴定法により希土類
元素を定量することによって及び酸に由来する１価陰イ
オンな逆酸滴定することによって決定される。The chemical composition of the colloid is determined on the residue obtained after centrifugation of the dispersion by quantifying rare earth elements by complexometric titration with EDTA and by reverse acid titration of monovalent anions derived from acids. .
この組成は、次の化学式（Ｔ）
ＴＲ（Ａ） 、 （Ｏ）Ｉ） ＄−ｘ （
Ｉ）（ここで、ＴＲは希土類元素、好ましくはイツトリ
ウム族陽イオンを表わし、
Ａは２．５〜５のｐＫａを有する水溶性の１価の酸の陰
イオンを表わし、
Ｘは２．５〜１、好ましくは１．１〜２．２、さらに好
ましくは１．２〜１．８の数である）に相当する。This composition has the following chemical formula (T) TR(A) , (O)I) $-x (
I) (wherein TR represents a rare earth element, preferably a yttrium group cation, A represents an anion of a water-soluble monovalent acid having a pKa of 2.5 to 5, and X represents a cation of a water-soluble monovalent acid having a pKa of 2.5 to 5. 1, preferably 1.1 to 2.2, more preferably 1.2 to 1.8).
本発明の好ましいゾルは、ＴＲがイツトリウム又はホル
ミウムを表わし、Ａが酢酸陰イオンを表わし、Ｘが１．
１〜２．２、好ましくは１．２〜１．８である式（１）
に相当する希土類元素化合物のゾルである。In a preferred sol of the present invention, TR represents yttrium or holmium, A represents an acetate anion, and X represents 1.
Formula (1) which is 1 to 2.2, preferably 1.2 to 1.8
It is a sol of a rare earth element compound corresponding to .
本発明によって得られるコロイドは球形状を呈する。The colloid obtained by the present invention has a spherical shape.
コロイドの大きさは、ミハエル・Ｌ・マコンネル氏によ
り「アナリチカル・ケミストリーＪ Ｖｏｌ。The size of colloids is explained by Michael L. McConnell in "Analytical Chemistry J Vol.
５３、Ｎｏ、８．１００７Ａ （１９８１）に記載の方
法による光の準弾性散乱によって決定されるコロイドの
流体力学的直径を測定することによって決められる。コ
ロイドの大きさは１０〜２０００人の間であり、そして
コロイドの流体力学的平均直径は３０〜１００Ａの間に
ある。53, No. 8.1007A (1981) by measuring the hydrodynamic diameter of the colloid as determined by quasi-elastic scattering of light. The size of the colloid is between 10 and 2000, and the average hydrodynamic diameter of the colloid is between 30 and 100A.
また、本発明の方法により得られるゾルは慣用の貯蔵条
件（この貯蔵は好ましくは周囲温度より低く、５〜１０
℃の間の温度で行われる）下で完全に安定であることが
認められる。The sols obtained by the process of the invention can also be stored under conventional storage conditions (storage preferably below ambient temperature, 5 to 10
It is found to be completely stable at temperatures between
本発明の方法で得られるゾルの性質は以下の実施例で立
証する。The properties of the sols obtained by the method of the invention are demonstrated in the following examples.
［実施例］
匠−ユ
温度計、攪拌装置、反応体導入系及び上向き冷却器を備
え、そして加熱装置及びｐＨ測定ユニットを取付けた２
℃の反応器に、１０００ｃｃの２Ｎ酢酸溶液を導入する
。[Example] 2 equipped with a Takumi-Yu thermometer, a stirring device, a reactant introduction system, and an upward condenser, and a heating device and a pH measuring unit.
1000 cc of 2N acetic acid solution is introduced into the reactor at .degree.
次いで、この媒質に、発光物質特級と称してロース・ブ
ーラン社より市販されている純度９９、９９％の酸化イ
ツトリウム１７３ｇ１ｌ械的に攪拌することによって分
散させる６
次いで、加熱を開始し、７０℃の温度になったならば、
この温度を３時間３０分維持する。Next, 173 g 1 l of yttrium oxide with a purity of 99, 99%, which is commercially available from Roos-Boulin under the name Luminescent Material Special Grade, is dispersed in this medium by mechanical stirring. If the temperature reaches
This temperature is maintained for 3 hours and 30 minutes.
イツトリウム化合物のゾルの生成が認められ、そして反
応しなかった酸化イツトリウムよりなる残渣の存在が認
められた。このものは後記のように分離し、場合によっ
ては浸蝕工程に再循環することができる。The formation of a sol of a yttrium compound was observed, and the presence of a residue consisting of unreacted yttrium oxide was observed. This can be separated as described below and optionally recycled to the erosion process.
反応媒質をジヨウアン式遠心分離機により３５００ ｒ
ｐｍで２０分間遠心操作に付す。The reaction medium was centrifuged at 3500 r
Centrifuge at pm for 20 minutes.
上澄液を取出す。Remove the supernatant.
その中に連行された大きな粒子な細孔直径が１μｍ以上
である微孔質濾紙で濾過することによって除去する。The large particles entrained therein are removed by filtration through a microporous filter paper with a pore diameter of 1 μm or more.
浸蝕反応率は９９％と決定された。The erosion reaction rate was determined to be 99%.
下記の化学式
％式％
に相当するイツトリウム化合物のゾルが得られた。この
ゾルはＹ２Ｏ３として表わして１８２ｇ／βの濃度及び
６．８のｐＨを有する。A sol of an yttrium compound corresponding to the following chemical formula % was obtained. This sol has a concentration of 182 g/β expressed as Y2O3 and a pH of 6.8.
コロイド形のイツトリウムの割合は、超遠心分離（４５
０００ｒｐｍ、１時間）した後に得られた上澄み溶液中
の全イツトリウムなＥＤＴＡ滴定溶液で錯滴定すること
により定量することによって決定される。上澄溶液から
のイツトリウムの定量によりコロイド形のイツトリウム
の割合が９５％と決定できた。The proportion of yttrium in colloidal form was determined by ultracentrifugation (45
000 rpm for 1 hour) and then complex titration with a total yttrium EDTA titration solution in the supernatant solution obtained. By quantifying yttrium from the supernatant solution, the proportion of yttrium in colloidal form was determined to be 95%.
また、コロイドの大きさは、ミハエル・Ｌ・マコンネル
氏により「マナリチカル・ケミストリーＪ Ｖｏｌ、
５３、Ｎｏ、８．１００７Ａ（１９８１）に記載の方法
に従う光の半弾性散乱により特徴づけられる。コロイド
の流体力学的平均直径は４１人程度である。The size of colloids is also explained by Michael L. McConnell in ``Manalytical Chemistry J Vol.
53, No. 8.1007A (1981). The average hydrodynamic diameter of the colloid is approximately 41 mm.
得られたゾルは５℃で少なくとも１ケ月の貯蔵安定性を
示すことが認められた。The resulting sol was found to exhibit storage stability for at least one month at 5°C.
匠−１
例１に記載のような反応器に１０００ｃｃの２Ｎ酢酸溶
液を導入する。Takumi-1 1000 cc of 2N acetic acid solution is introduced into a reactor as described in Example 1.
この媒質に、発光物質特級と称してロース・ブーラン社
より市販されている純度９９．９９％の酸化イツトリウ
ム１７３ｇを機械的に攪拌させることにより分散させる
。In this medium, 173 g of yttrium oxide with a purity of 99.99%, which is commercially available from Roth-Boulin under the name Luminescent Material Special Grade, is dispersed by mechanical stirring.
次いで、加熱を開始し、そして１００℃の温度になった
ならばこの温度を１時間保持する。Heating is then started and once a temperature of 100° C. is reached, this temperature is maintained for 1 hour.
イツトリウム化合物のゾルの生成が認められる。Formation of yttrium compound sol is observed.
浸蝕反応率は９９％と決定された。The erosion reaction rate was determined to be 99%.
次の化学式
％式％
に相当するイツトリウム化合物のゾルが得られた。この
ゾルはＹ２Ｏ，として表わしてｘ８２ｇ／ρの濃度及び
６．７のｐＨを有する。A sol of an yttrium compound corresponding to the following chemical formula % was obtained. This sol has a concentration expressed as Y2O of x82 g/ρ and a pH of 6.7.
コロイド形のイツトリウムの割合は９５％である。The proportion of yttrium in colloidal form is 95%.
コロイドの流体力学的平均直径は４３人である。The average hydrodynamic diameter of the colloid is 43 mm.
得られたゾルは５℃で少なくとも１ケ月の貯蔵安定性を
示した。The resulting sol exhibited storage stability for at least 1 month at 5°C.
鮭−旦
例１に記載のような反応器に、１０００ｃｃの２Ｎ酢酸
溶液を導入する。1000 cc of 2N acetic acid solution is introduced into a reactor as described in Example 1.
この媒質にロース・ブーラン社より市販されている純度
９９．９９％の酸化ホルミウム２９０ｇを機械的に攪拌
することにより分散させる。290 g of 99.99% pure holmium oxide, commercially available from Loos-Boulin, is dispersed in this medium by mechanical stirring.
次いで、加熱を開始し、そして７０℃の温度になったな
らばこの温度を３時間３０分保持する。Heating is then started and once a temperature of 70° C. is reached, this temperature is maintained for 3 hours and 30 minutes.
ホルミウム化合物のゾルの生成が認められ、そして反応
しなかった酸化ホルミウムよりなる残渣の存在も認めら
れた。後者は下記のように分離し、要すれば浸蝕工程に
再循環することができる。The formation of a holmium compound sol was observed, and the presence of a residue consisting of unreacted holmium oxide was also observed. The latter can be separated as described below and recycled to the erosion process if desired.
反応媒質をジヨウアン式遠心分離機により３５００ ｒ
ｐｍで２０分間遠心操作に付す。The reaction medium was centrifuged at 3500 r
Centrifuge at pm for 20 minutes.
上澄液を取出す。Remove the supernatant.
この上澄液に連行された大きい粒子な細孔直径が１μｍ
以上の微孔質濾紙で濾過することによって除去する。The diameter of the large particles entrained in this supernatant is 1 μm.
It is removed by filtration with the above microporous filter paper.
浸蝕反応率は９９％と決定された。The erosion reaction rate was determined to be 99%.
次の化学式 ％式％ に相当するホルミウム化合物のゾルが得られた。the following chemical formula %formula% A sol of a holmium compound corresponding to was obtained.
このゾルはＨｏｗｌｓとして表わして２９０ｇ／βの濃
度及び７．１のｐＨを有する。This sol has a concentration expressed as Howls of 290 g/β and a pH of 7.1.
コロイド形のホルミウムの割合は８２％である。The proportion of holmium in colloidal form is 82%.
コロイドの流体力学的平均直径は４５人である。The average hydrodynamic diameter of the colloid is 45 mm.
得られたゾルは５℃で少なくとも１ケ月の貯蔵安定性を
示した。The resulting sol exhibited storage stability for at least 1 month at 5°C.
Claims (1)
有する水溶性の１価の酸の所定量と反応させ、次いで得
られた反応媒質を加熱することからなることを特徴とす
る希土類元素化合物を水性媒質中に分散させてなるコロ
イド分散体の製造方法。 ２）希土類元素酸化物がイットリウム族希土類元素の酸
化物であることを特徴とする請求項１記載の方法。 ３）希土類元素酸化物が酸化イットリウム又は酸化ホル
ミニウムであることを特徴とする請求項２記載の方法。 ４）希土類元素酸化物が９９〜９９．９９％の純度を示
すことを特徴とする請求項１〜３のいずれかに記載の方
法。 ５）希土類元素酸化物を８５０℃〜１０５０℃の間の温
度での焼成操作に付すことを特徴とする請求項１〜４の
いずれかに記載の方法。 ６）焼成温度が約９５０℃であることを特徴とする請求
項５記載の方法。 ７）焼成時間が２〜４時間であることを特徴とする請求
項５又は６記載の方法。 ８）使用する酸が酢酸であることを特徴とする請求項１
〜７のいずれかに記載の方法。 ９）酸の溶液の濃度が１〜４Ｎの間で選ばれることを特
徴とする請求項１〜８のいずれかに記載の方法。 １０）酸の使用量が、使用する酸と希土類元素酸化物（
金属陽イオンとして表わして）との間のモル比が２．５
〜１であるような量であることを特徴とする請求項１〜
９のいずれかに記載の方法。 １１）モル比が１．１〜２．２であることを特徴とする
請求項１０記載の方法。 １２）モル比が１．２〜１．８であることを特徴とする
請求項１〜１１のいずれかに記載の方法。 １３）所望濃度の１価の酸の水溶液に希土類元素酸化物
を添加することを特徴とする請求項１〜１２のいずれか
に記載の方法。 １４）希土類元素酸化物を水に懸濁させ、次いで酸を適
切な量で添加することを特徴とする請求項１〜１２のい
ずれかに記載の方法。 １５）反応媒質を５０℃からその反応媒質の還流温度ま
での間の温度で熱処理に付すことを特徴とする請求項１
〜１４のいずれかに記載の方法。 １６）熱処理温度が７０〜１００℃であることを特徴と
する請求項１５記載の方法。 １７）反応温度を１〜４時間保持することを特徴とする
請求項１５又は１６記載の方法。１８）反応温度を３〜
４時間保持することを特徴とする請求項１７記載の方法
。 １９）残渣をろ過、デカンテーション又は遠心分離によ
って分離することを特徴とする請求項１〜１８のいずれ
かに記載の方法。 ２０）次の化学式（ I ） ＴＲ（Ａ）＿ｘ（ＯＨ）＿３＿−＿ｘ（ I ）（ここで
、ＴＲは希土類元素陽イオンを表わし、Ａは２．５〜５
のｐＫａを有する水溶性の１価の酸の陰イオンを表わし
、 ｘは２．５〜１の数である） に相当する希土類元素化合物を水性媒質中に分散させて
なる新規なコロイド分散体。 ２１）ＴＲがイットリウム族希土類元素を表わすことを
特徴とする請求項２０記載のコロイド分散体。 ２２）ＴＲがイットリウム又はホルミウムを表わすこと
を特徴とする請求項２１記載のコロイド分散体。 ２３）Ａが酢酸陰イオンを表わすことを特徴とする請求
項２０〜２２のいずれかに記載のコロイド分散体。 ２４）ｘが１．１〜２．２であることを特徴とする請求
項２０〜２３のいずれかに記載のコロイド分散体。 ２５）ｘが１．２〜１．８であることを特徴とする請求
項２４記載のコロイド分散体。 ２６）コロイドが球形状であることを特徴とする請求項
２０〜２５のいずれかに記載のコロイド分散体。 ２７）コロイドの流体力学的平均直径が３０〜１００Å
にあることを特徴とする請求項２０〜２６のいずれかの
記載のコロイド分散体。 ２８）コロイド形の希土類元素の割合が８５〜１００％
であることを特徴とする請求項２０〜２７のいずれかに
記載のコロイド分散体。 ２９）希土類元素酸化物として表わして１モル／ｌにも
なり得る高い希土類元素化合物濃度を有することを特徴
とする請求項２０〜２８のいずれかに記載のコロイド分
散体。 ３０）６．０〜７．５のｐＨを示すことを特徴とする請
求項２０〜２９のいずれかに記載のコロイド分散体。[Claims] 1) Reacting a rare earth element oxide with a predetermined amount of a water-soluble monovalent acid having a pKa between 2.5 and 5.0, and then heating the resulting reaction medium. A method for producing a colloidal dispersion comprising dispersing a rare earth element compound in an aqueous medium. 2) The method according to claim 1, wherein the rare earth element oxide is an oxide of an yttrium group rare earth element. 3) The method according to claim 2, wherein the rare earth element oxide is yttrium oxide or forminium oxide. 4) The method according to any one of claims 1 to 3, characterized in that the rare earth element oxide exhibits a purity of 99 to 99.99%. 5) Process according to any one of claims 1 to 4, characterized in that the rare earth element oxide is subjected to a calcination operation at a temperature between 850°C and 1050°C. 6) The method according to claim 5, characterized in that the calcination temperature is about 950°C. 7) The method according to claim 5 or 6, characterized in that the firing time is 2 to 4 hours. 8) Claim 1 characterized in that the acid used is acetic acid.
8. The method according to any one of . 9) Process according to any of claims 1 to 8, characterized in that the concentration of the acid solution is chosen between 1 and 4N. 10) The amount of acid used depends on the acid used and the rare earth element oxide (
(expressed as metal cations) is 2.5
Claim 1~ characterized in that the amount is such that ~1.
9. The method according to any one of 9. 11) The method according to claim 10, characterized in that the molar ratio is 1.1 to 2.2. 12) The method according to any one of claims 1 to 11, characterized in that the molar ratio is 1.2 to 1.8. 13) The method according to any one of claims 1 to 12, characterized in that the rare earth element oxide is added to an aqueous solution of a monovalent acid at a desired concentration. 14) Process according to any one of claims 1 to 12, characterized in that the rare earth element oxide is suspended in water and then an appropriate amount of acid is added. 15) Claim 1 characterized in that the reaction medium is subjected to a heat treatment at a temperature between 50°C and the reflux temperature of the reaction medium.
15. The method according to any one of 14 to 14. 16) The method according to claim 15, wherein the heat treatment temperature is 70 to 100°C. 17) The method according to claim 15 or 16, characterized in that the reaction temperature is maintained for 1 to 4 hours. 18) Adjust the reaction temperature to 3~
18. The method according to claim 17, characterized in that the holding time is 4 hours. 19) A method according to any one of claims 1 to 18, characterized in that the residue is separated by filtration, decantation or centrifugation. 20) The following chemical formula (I) TR(A)_x(OH)_3_-_x(I) (here, TR represents a rare earth element cation, and A is 2.5 to 5
A novel colloidal dispersion obtained by dispersing in an aqueous medium a rare earth element compound corresponding to the anion of a water-soluble monovalent acid having a pKa of , x is a number from 2.5 to 1. 21) The colloidal dispersion according to claim 20, wherein TR represents an yttrium group rare earth element. 22) The colloidal dispersion according to claim 21, wherein TR represents yttrium or holmium. 23) A colloidal dispersion according to any one of claims 20 to 22, characterized in that A represents an acetate anion. 24) The colloidal dispersion according to any one of claims 20 to 23, wherein x is 1.1 to 2.2. 25) The colloidal dispersion according to claim 24, wherein x is 1.2 to 1.8. 26) The colloid dispersion according to any one of claims 20 to 25, wherein the colloid has a spherical shape. 27) The average hydrodynamic diameter of the colloid is 30-100 Å
The colloidal dispersion according to any one of claims 20 to 26, characterized in that: 28) The proportion of rare earth elements in colloidal form is 85-100%
The colloidal dispersion according to any one of claims 20 to 27, characterized in that: 29) Colloidal dispersion according to any of claims 20 to 28, characterized in that it has a high concentration of rare earth compounds, expressed as rare earth oxides, which can be as high as 1 mol/l. 30) The colloidal dispersion according to any one of claims 20 to 29, which exhibits a pH of 6.0 to 7.5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8712669A FR2620437B1 (en) | 1987-09-14 | 1987-09-14 | PROCESS FOR OBTAINING COLLOIDAL DISPERSION OF A RARE EARTH COMPOUND IN AQUEOUS MEDIA AND PRODUCT OBTAINED |
| FR87/12669 | 1987-09-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01294521A true JPH01294521A (en) | 1989-11-28 |
| JPH0761864B2 JPH0761864B2 (en) | 1995-07-05 |
Family
ID=9354847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63228911A Expired - Fee Related JPH0761864B2 (en) | 1987-09-14 | 1988-09-14 | Process for producing aqueous colloidal dispersion of rare earth element compound and product thereof |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5716547A (en) |
| EP (1) | EP0308311B1 (en) |
| JP (1) | JPH0761864B2 (en) |
| AT (1) | ATE78798T1 (en) |
| AU (1) | AU623087B2 (en) |
| BR (1) | BR8804714A (en) |
| CA (1) | CA1303940C (en) |
| DE (1) | DE3873233T2 (en) |
| ES (1) | ES2042786T3 (en) |
| FR (1) | FR2620437B1 (en) |
| GR (1) | GR3005887T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03232721A (en) * | 1989-12-15 | 1991-10-16 | Rhone Poulenc Chim | Preparation of colloidal dispersing element of cerium iv compound in aqueous medium and dispersing element thus obtained |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2734560B1 (en) * | 1995-05-24 | 1997-08-14 | Rhone Poulenc Chimie | COMPOUND BASED ON YTTRIUM OR REDISPERSIBLE HOLMIUM IN THE FORM OF A SOIL |
| FR2736042B1 (en) * | 1995-06-30 | 1997-09-12 | Rhone Poulenc Chimie | COLLOIDAL DISPERSION AND REDISPERSIBLE COMPOSITION IN THE FORM OF A COLLOIDAL DISPERSION BASED ON CERIUM OXIDE |
| FR2801299B1 (en) * | 1999-11-23 | 2002-06-07 | Rhodia Terres Rares | AQUEOUS COLLOIDAL DISPERSION BASED ON AT LEAST ONE COMPOUND OF A LANTHANIDE AND A COMPLEXANT, METHOD OF PREPARATION AND USE |
| FR2817771B1 (en) * | 2000-12-08 | 2003-11-28 | Rhodia Terres Rares | COLLOIDAL RARE EARTH PHOSPHATE DISPERSION AND PREPARATION METHOD |
| FR2817770B1 (en) * | 2000-12-08 | 2003-11-28 | Rhodia Terres Rares | AQUEOUS COLLOIDAL DISPERSION OF RARE EARTH PHOSPHATE AND PREPARATION METHOD |
| US20030032679A1 (en) | 2001-06-20 | 2003-02-13 | Cayton Roger H. | Non-aqueous dispersion of nanocrystalline metal oxides |
| US7229600B2 (en) * | 2003-01-31 | 2007-06-12 | Nanoproducts Corporation | Nanoparticles of rare earth oxides |
| WO2021171724A1 (en) * | 2020-02-28 | 2021-09-02 | 株式会社村田製作所 | Metal double salt liquid dispersion, method for producing metal double salt liquid dispersion, metal oxide nanoparticle liquid dispersion, and method for producing metal oxide nanoparticle liquid dispersion |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62209039A (en) * | 1986-03-08 | 1987-09-14 | Taki Chem Co Ltd | Aqueous solution of basic yttrium acetate and production thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3024199A (en) * | 1958-09-02 | 1962-03-06 | Du Pont | Stable aquasols of hydrous rare earth oxides and their preparation |
| US3082103A (en) * | 1959-11-12 | 1963-03-19 | Horizons Inc | Stable colloidal dispersions and method of preparing same |
| US3148151A (en) * | 1962-02-22 | 1964-09-08 | Grace W R & Co | Method of preparing rare earthactinide metal oxide sols |
| US3476691A (en) * | 1964-09-23 | 1969-11-04 | Atomic Energy Commission | Process for preparing an yttria aquasol |
| US4181532A (en) * | 1975-10-22 | 1980-01-01 | United Kingdom Atomic Energy Authority | Production of colloidal dispersions |
| WO1979000248A1 (en) * | 1977-11-01 | 1979-05-17 | Atomic Energy Authority Uk | Production of dispersions |
| US4356106A (en) * | 1980-05-09 | 1982-10-26 | United Kingdom Atomic Energy Authority | Cerium compounds |
| US4647401A (en) * | 1983-01-24 | 1987-03-03 | Rhone Poulenc Inc. | Process for preparing colloidal ceric oxide and complexes thereof with free organic acids |
| US4770671A (en) * | 1985-12-30 | 1988-09-13 | Minnesota Mining And Manufacturing Company | Abrasive grits formed of ceramic containing oxides of aluminum and yttrium, method of making and using the same and products made therewith |
| US4801399A (en) * | 1986-02-25 | 1989-01-31 | University Of Florida | Inorganic salts as peptizing agents in the preparation of metal oxide sol-gel compositions |
| FR2621576B1 (en) * | 1987-10-09 | 1990-01-05 | Rhone Poulenc Chimie | COLLOIDAL DISPERSION OF A CERIUM IV COMPOUND IN AN AQUEOUS MEDIUM AND ITS PREPARATION METHOD |
| FR2640611A1 (en) * | 1988-12-16 | 1990-06-22 | Rhone Poulenc Chimie | RARE EARTH OXIDE WITH NEW MORPHOLOGICAL CHARACTERISTICS AND METHOD OF OBTAINING THE SAME |
| FR2655972B1 (en) * | 1989-12-15 | 1992-04-24 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF A COLLOUIDAL DISPERSION OF A CERIUM IV COMPOUND IN AQUEOUS MEDIA AND DISPERSIONS OBTAINED. |
-
1987
- 1987-09-14 FR FR8712669A patent/FR2620437B1/en not_active Expired - Lifetime
-
1988
- 1988-09-12 EP EP88402292A patent/EP0308311B1/en not_active Expired - Lifetime
- 1988-09-12 DE DE8888402292T patent/DE3873233T2/en not_active Expired - Lifetime
- 1988-09-12 AT AT88402292T patent/ATE78798T1/en not_active IP Right Cessation
- 1988-09-12 ES ES88402292T patent/ES2042786T3/en not_active Expired - Lifetime
- 1988-09-13 BR BR8804714A patent/BR8804714A/en not_active IP Right Cessation
- 1988-09-13 CA CA000577276A patent/CA1303940C/en not_active Expired - Lifetime
- 1988-09-13 AU AU22180/88A patent/AU623087B2/en not_active Ceased
- 1988-09-14 JP JP63228911A patent/JPH0761864B2/en not_active Expired - Fee Related
-
1992
- 1992-10-05 GR GR920402218T patent/GR3005887T3/el unknown
-
1993
- 1993-05-03 US US08/055,772 patent/US5716547A/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62209039A (en) * | 1986-03-08 | 1987-09-14 | Taki Chem Co Ltd | Aqueous solution of basic yttrium acetate and production thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03232721A (en) * | 1989-12-15 | 1991-10-16 | Rhone Poulenc Chim | Preparation of colloidal dispersing element of cerium iv compound in aqueous medium and dispersing element thus obtained |
Also Published As
| Publication number | Publication date |
|---|---|
| US5716547A (en) | 1998-02-10 |
| AU2218088A (en) | 1989-03-16 |
| CA1303940C (en) | 1992-06-23 |
| DE3873233D1 (en) | 1992-09-03 |
| FR2620437B1 (en) | 1990-11-30 |
| DE3873233T2 (en) | 1992-12-10 |
| JPH0761864B2 (en) | 1995-07-05 |
| BR8804714A (en) | 1989-04-18 |
| ATE78798T1 (en) | 1992-08-15 |
| GR3005887T3 (en) | 1993-06-07 |
| EP0308311B1 (en) | 1992-07-29 |
| EP0308311A1 (en) | 1989-03-22 |
| ES2042786T3 (en) | 1993-12-16 |
| AU623087B2 (en) | 1992-05-07 |
| FR2620437A1 (en) | 1989-03-17 |
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